Process for preparing petroleum resins ii



uly 14, 1959 F. w. BANES ET AL 2,894,937

PROCESS FOR PREPARING PETROLEUM RESINS :1

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} J' ph fhiim 'jnventors Pobert Learg B16 cLttorne United States Patent 2,894,937 I PROCESS FOR PREPARING PETROLEUM RESINS II F. Nelson, Westfield, and

N.J., assignors to Esso Rea corporation of Fred W. Banes and Joseph Robert F. Leary, Cranford, search and Enginering Company, Delaware Continuation of application Serial No. 318,222, November 1, 1952. 581,943

1 Claim. (Cl. 260-82) This invention is concerned with the production of light colored, high quality resins from unsaturated petroleum fractions obtained by steam cracking and, more particularly, with the production of resins from a fraction largely free of cyclic dienes and materials boiling This application May 1, 1956, Serial No.

below 38 0., including isoprene, by the use of an I aluminum halide catalyst in the solid, finely divided state and slurries or solutions thereof. The polymerization process also incidentally produces fractions having relatively high aromatic content from which chemiresins, and at the same time, yield by-product streamsf which are free of sludge forming components but contain high concentrations of the desired aromatics.

The invention is of especial importance as a valuable process for the production of light colored, unsaturated resins from the highly unsaturated petroleum fractions produced by steam cracking. Preferably, the cyclic dioleiins, such as cyclopentadiene and methylcyclopentadiene, are removed from a steam cracked fraction boil-' ing substantially below C At least 50% up to all of the isopreue containing fraction present and boiling from the initial boiling point up to 38 C. is also removed.

The cyclic diolefins, including cyclopentadiene and methv yl cyclopentadiene, are preferably removed by dimerization and distillation. The isoprene fraction is either completely removed or the isoprene content is adjusted by fractional distillation and/ or suitable blending of streams.

The resulting stream is a fraction boiling below C or v C and is polymerized at approximately room tempera ture with an aluminum halide catalyst as the solid, as a slurry or in solution. Conversions of 10% to 40% of the prepared feed to resins are obtained.

V Distillation Range rcornpositlon, Wt. percent:

points. They are of particular use in printing ink formulations, as rubber compounding ingredients, and'for blending with high softening point resins in the preparation of floor tile. 7

Petroleum fractions such as kerosene, gas oil, naphtha, etc. are cracked in the presence of steam at temperatures above 1000 F. up to 1500 F. to give unsaturated product stream. The liquid cut boiling mostly below about C but containing components up to C is segregated and heated at about to 140 C. to dimerize cyclopentadienes. Thereafter, a C to C and lighter liquid cut is taken overhead to separate dimer concentrates as bottoms. The overhead stream, substantially freed of cyclodienes, is then fractionated to remove at least half of the isoprene containing fraction boiling below 38 C. and is the raw material for making these superior resins. I Table I shows the preferred specifications for the resin feed streams, showing both distillation ranges and chemical composition. Table II shows the compositions of typical feed streams. Naphtha samples B, C, D, F and Gare selected from within the specification limits of Table I and represent desirable feed streams for use in carrying out the invention. Stream samples A and E are representative of naphthas having undesirable characteristics for the preparation of resins.

TABLE I Specifications for resin feed streams [Boiling range 20-140" 0., predominantly 30130 O. and containing 15 Wt. percent or less boiling below 38 0. (including 3.5 Wt. percent or less isoprene on the total stream) 35-70 Wt. percent. 5.

Aromatics Benzene Tnlnene Ca Aromatics The diolefin content of this mixture was obtained by reacting a mixture of 1.5 to 3.0 ml. of sample and 2.5 ml.

1 of chloromaleicanhydride (diluted with 2 ml. benzene Theseresins are light colored and have high softening containing 0.1% tertiary butyl catechol) for 3 .hours at C., and steam distilling the resulting reaction mixture, for 2 hours to recover HCl (1 mole/mole of di olefin)..

TABLE II COMPOSUIOIL of typical resm feed streams Naphtha A B C D E F G Distillation:

Wt. Percent Overhead: I.B.P. to 38 C. 29 13. 5 3. 5 3. 9 17 8 38-70 28 32.5 39 39.9 22 25 31 70-130 42 53 54. 52. 7 69 64 69 0+. 1 1 3.0 3.5 2 3 1 Composition, Wt.

D101 fin 18.2 19. 4 16. 2 14. 5 14 19 7.0 3.1 1 1 40 1 1 6.9 8.8 9.8 8.3 7.5 8.3 1. 0 1. 0 1.8 1. 2 0. 7 0. 9 1 3. 3 6. 5 4. 6 3. 5 2. 3 4.8 Aromatics- 14. 5 19. 2 22. 1 19.6 20 29. 1 30 5.7 7.4 8.1 4.2 9 6.8 8 1 1 1 1 1 1 1 Paraflins 2 3 3 1 1 1 2 Olefins 59.6 51 50.6 60.2 55.5 49.1 41

The selected streams are treated with an aluminum 20 500 parts of unsaturated feed was agitated at 20 to halide catalyst at about 40 to +70 C., preferably 0 to -+50 'C., under conditions of good agitation. The resin thus formed may be recovered by water and/or alkali washing to remove catalyst, followed by stripping off the unpolymerized material. One good way to remove the catalyst is to add methyl alcohol to form a solid complex with AlCl which is then filtered off. However, other methods for removing the catalyst from the polymerized products may be used.

The washed resin solutions are then stripped of unreacted hydrocarbons boiling up to the end point of the feed naphtha, about 140 C. The resulting crude resin concentrate is then stripped under vacuum or with steam to remove liquid polymer and to recover a solid resin product having a softening point of 80 C. or higher. Such a resin product, for example, might be obtained by stripping to a bottoms temperature of 260 to 270 C. at a pressure of 2 to 5 mm. Hg.

The yield of liquid polymer boiling between the hydrocarbon feed naphtha and the resin is dependent on the .feed composition, catalyst concentration and temperature. It is desirable that the yield of liquid polymer beheld to 7% or less on'the feed since it is essentially C. While 5 parts of powdered AlCl was added over a period of 30 minutes. The agitation was continued for an additional 60 minutes .at C. after which the reactor contents were washed with 5% H SO solution and then with water at temperatures of about C. The naphtha was stripped 011 at atmospheric pressure and the remaining crude resin was stripped to .a bottoms temperature of 270 C. at 2 to 5 mm. Hg to give a light colored 'res'in product. The data from this series of runs is tabulated in Table III below.

These data show that feeds having 13.5 wt. percent or less of the *isopreLe-containing fraction give resin yields of 35.2 to 37.1 wt. percent at a resin softening point of 90 C. In each case the yield of liquid polymer is low at 3.7 'to 5.2%. However, the feed (A) containing more than 15% of the isoprene-containing fraction gave loweryields (31.5 to 32.2%) and also excessively high liquid polymer yields (810%). This latter feed also produced insoluble gel in contrast to the completely soluble products produced with feeds C and B.

The light color of these resins is also particularly useless and represents a complete loss of feed comdesil'abley afe'genefally of'li'ght amber'colol and ponents. 45 have Gardner colors of 2 to 3.

TABLE III Efiect of I.B'.'P;38 C. concentration on liquid polymer yield Feed (Table II) 0 B A Wt. Percent I.B.P.38 G. Fraction 3.5 13.5 29

Wt. Percent Isoprene on Feed 1 3.1 6.7

Percent A101; 011 Feed 0. 7 5 1.0 0. 75 1.0 0. 75 1.0 1.2 5 Resin Yield. Wt. Percent. 35. 2 37. 1 35. 7 35. 9 32. 2 31. 5 31. 5 Liquid Polymer, Wt. Percent 4. 7 3. 7 '5. 2 4. 9 8. 4 8.8 10. 3 Gel., Wt. Percent 1-2 '1-2 I-2 Resin Soft. Pt., C. 92 90 90 90 90 89 90 0101 7 3 2 3 2 2 3 3 Iodine N 0 5 202 204 205 197 202 1 Ring and Ball Softening Point (ASTM E28-51-T). I Gardner color index, 1 g. resin/67 g. xylene. 8 ASTM (D555-47).

Over a catalystconcentration range of 0.5 to 5% and a temperature range of -40 to +70 'C., the yield of liquid polymer is at a desirably low level provided the isoprene fractions of the feed (20'38 C. fraction) represent approximately 15% or less of the total feed.

It is to be understood that this polymerization process can be carried out either in a batch or continuous manner.

The invention is described in more complete detail by the "following examples and the accompanying figures, although it is not intended to limit the scope of the invention thereto.

EXAMPLE I A'series of comparative runs were carried out using feed stock as identified in Table II. In each experiment,

EXAMPLE II 5 the amount of liquid p'oly'mer also increases; At the level of about 3.0% AlCl catalyst, the amount'of liquid polymer is within allowable limits. Feeds containing 18% and above of the isoprene fraction gave partially insoluble resins and high amounts ofliquid polymer. 5

TABLE IV 3 resins having high qualities in every way. Low amounts of liquid polymer were also shown. Temperatures below C. gave somewhat reduced yields of resin but having good qualities and accompanied by only small amounts of liquid polymer.

Addition of l.B.P.-38? C. (isopfene containing) fraction to basic feed The effects of temperature on the polymerization re- 70 action are shown in Table VI. Aluminum chloride powder of 30 mesh was employed with a constant feed using reaction temperatures varying from -40 C. up to +50 C. Details are shown in Table VI. Temperatures of about 0 C. up to 50 C. gave uniformly high yields and 75 Feed l) (Table II), Wt. Percent v 100 1 100 100 100 95 90 85 8O 75 Wt. Percent I.B.P.-3s O 0 0 0 0 5 Total I.B.P.-38 6. Out 3.9 3.9 3.9 3.9 8.8 13.5 18.3 23 1 27.9 Percent A101, 1 1. 5 2. 0 3. 0 1 1 1 1 Temperature Catalyst added over 34 hour period at 20-25 C. Time. r Reaction mixture then agitated for one no r at 5 C. Resin, Wt. Percent -32.2 31.5 33.3 33.2 32.2 30.6 31.4 32.2 31.9 Liquid Polymer, Wt. Percent. 3. 8 .4. 7 5. 3 6. 6 4. 8 5.6 7. 1 7.8 8. 1 R i(gel. Wt. Percent None None None None None None 1-4 14 1-4 Softening Point 90 87 90 90 86 89 90 90 91 Color.. 3 4 3 4 4 3 2 3 4 3 Iodine Number 183 150 186 173 188 188 EXAMPLE III TABLE VII A series of experiments was carried out to study the Study of temperature eflect effect of variations in the physical form of AlCl and the manner in which it iS added. In this study, both NaphthaFe9d(Tab1e11) D 30 mesh and 100 mesh solid AlCl were tested and used as catalysts. In addition, 30 mesh AlCl was slurried in Catalyst A101 Powder 30 Mesh) several different liquid media, including the polymerization reactor efiluent, the polymerizate, a mixture of 32 l go gl lg e en aged 1. g 1. g 1 8 1. 8

t s i 1 m xylenes, and the raffinate. Details of the experiments i 4H0 20.25 0 are shown in Table V. The resulting resins were obtained l Percent on Fe 32 5 32 2 29 8 18 in good yields and were of uniform good quality with lliquid lol yr nerjln 413 318 512 5.4 respect to both softening point and color. The poly- 40 ,o 9O 90 go 89 merization reactions showed very low amounts of the Color 2 3 3 2 undesirable liquid polymer products.

TABLE V Study of catalyst efiect Naphtha Feed (Table II) p B Catalyst Powdered A101; Slurried 30 Mesh A101; (35% Solids) Reactor Washed 100 Mesh 30 Mesh Efliuent Poly- Xylenes Rafiinate merlzate v Wt Percent A1013 on Feed 0. 0. 75 1.0 1. 0 1. 0 1. 0 1. 0

l 0118. g1 3- l0Il I 2 2 Yields, Wt. Percent on Feed:

Resin 35. 7 33.7 33. 2 32. 4 33. 2 32. 6 32. 5

Liquid Polymer 5. 2 5.6 5. 4 5. 4 5. 6 5.8 5. 5 Resin:

Soft. Pt "0 89 88 9o 88 88 90 Color 4 4 2 3 3 3 3 1 30 min. at 20 C. 60 min. at 45 0.

EXAMPLE IV EXAMPLE V Experiments were carried out using the aluminum halides in solution as catalysts. Both AlCl dissolved in ethyl chloride and AlBr dissolved in n-hex-ane gave excellent yields of high quality resins and relatively small amounts of liquid polymer.

The data of the experiments are shown in Table VII.

7 TABLE VI! Feed (Table II) A1013 AIBIg. 1.0. 1.0.

Ethyl Chlo- Solution in ride Solun-Hexane tion.

Iodine Number Wt. Percent Liquid Polymer EXAMPLE VI Table VIII shows that the aluminumhalides, specificially AlCl and AlBr are in every case greatly superior to BF as catalysts for producing high quality resins. The BF catalyst gives resin having much lower softening point and much higher unsaturation as shown by the iodine number values. Also, the BE, catalyst gives approximately three times as much of the undesirable liquid polymer as does the aluminum halide catalyst.

tion as stream. 22. The process may .be operated either atchwseor a c ntinuous ma n EXAMPLE VIII n asecond em dim nt, wn schemat cal y .in ure 2, the invention is'carried out according to the fol lowing description. The polymerization, using an A101 catalyst, is used as a means not only for separating relatively pure chemical fractions and for preparing an arcmatic extraction feed stock 'but also as a means of prepan'ng useful and Valuable resins using either AlCl or AlBr catalyst.

The polymerization process involves the addition of A101 or AI-BI} catalyst to an unsaturated distillate from t am ac g operations from which the t e cyc pentadienes have been largely removed and which has been adjusted as t conten of the isomeric -,c n aining fraction boiling from 2040 38* -C. The steam cracked distillate streams il and 53 from steam cracking sources 50 and 54- either may or may not be subjected to a distillation tower 52 to remove an isoprene containing s t-ream 56, thereby allowing any desired amount of the .I.B.P. -38 C. isoprene fraction to remain in combined stream .57. .Streams.51.and.55..are .combinedas stream 57 and taken to a thermal soaker 58 for dimerization at 90 Details are shown in Table VIII. 25 to 140 C. The stream 59 from the thermal soaker 58 TABLE VIII Comparison of aluminum halides with BF;

Feed (Table II) F G Catalyst A1 1; A1 1; AlBr; BF; A101; Weight Percent on Feed 1.0 1.0 1.0 1.0 1.0 Method of Addition 30 es 0% lurry I Solution in Gas 30 Mesh Powder in n-Hexane n-Hexane Powder Reaction Temperature, 0..-. 20 100 25. 20 I 30-35 .25 Reaction Time, min 60 60 60 60 60 60 Resin Yield, Wt. Percent on Fee 27. 7 19. 4 25. 5 25.3 25 2 .4 Softening Point, C 9 '60 86 9O 44' 39 Color 3 4 p '2 ,3 2 4 Iodine Number 215 208 259 214 Wt. Percent Liquid Polymer 5.2 4. 7 3. 2 13. 4 4.4

EXAMPLE VII To illustrate one embodiment of the invention in a 4 schematic manner, Figure l is presented. A steam cracked distillate of boiling range 20 to 140 C. is taken from storage 1 via line 2 to a thermal soaker 3 in which a temperature of 90 to 140 C. is maintained. Following this thermal treatment to convert the cyclic dienes to dimers, the mixture is removed via line 4 and subjected to a steam or vacuum distillation tower 5 from which the cyclopentadiene dimers are removed as a concentrate stream 6. Either a part of all of the ,undimerized portion, C -C is passed as stream :7 to .a fractionation tower 10, from which an isoprene containing fraction boiling from 20 to 38 C. is removed as an overhead stream 9. To adjust isoprene content in the polymerization zone, a part of stream 7 can bypass tower via line 8 and go directly to polymerization reactor 12. A stream boiling from 20 to 140 C. is taken from the lower portion of tower 10 and passed by line 11 to polymerization reactor 12. The AlCl catalyst is added via inlet 13. The olefinic-feed stream is subjected to polymerization in reactor 12 at temperatures of from 0 to 60 C. The polymerized reaction mixture is passed by line 14 through a catalyst removal zone 15 from which catalyst is removed by line 16. The polymerized stream 17 is taken to an atmospheric distillation tower 18. From this distillation tower 18, a C C overhead stream 19 is removed and can be utilized for isolating aromatic components and the like. A crude resin fraction 20 is passed to a distillation tower 21 equipped forsteamand/ or vacuum'distillation from which .a small amount of liquid polymer, is removed as overhead stream 24 and .the finished resin product is removed from the bottom poris passed to distillation tower 60 by line 59 to remove head stream of C -C olefins as stream 61 which is passed to the polymerization reactor 63. The amount of AlCl catalyst added by line .162 represents 0.5 to 5.0 weight percent on the feed and is used in amounts that are necessary to convert from 10% to 50%, and preferably 15 to 35%, of the olefinic hydrocarbon feed material to resins. This polymerization can be carried out as a batch or continuous process at temperatures in the range of -40 to +70 C. In either operation, the reaction mixture from the polymerization step is passed by line 64 and is sent to a settler 65 to separate any insoluble products or catalyst complexes (if formed) as stream 66.

The supernatent layer from settler 65 is then sent as streamt67 to =a. cat alyst remov al unit 68 for removing any residual catalyst .as stream 69. This catalyst removal may be accomplished in ;a number of 'ways .e.g. water or caustic washing, precipitation of a CH OH.AlC-l complex followed by filtration, adsorption of active catalyst on .a solid basic material, etc.

The polymerization reaction product, freed ofcatalyst, is next taken by line 70 to an atmospheric distillation tower 72 and stripped to remove unreacted hydrocarbon material, C C boiling below about C., as stream 71 and the crude resinis taken by line 73 to column 74 where it 'is stripped further with steam or inert gas or under vacuum to remove low molecular weight liquid polymer products or small quantities of materials boiling as stream'75, while the finished resin is removed as b ot toms stream '76. One such finishing operation is a flash distillation under vacuum to a bottoms (resin) temperature of 250 to 270 C. at 2 to 4 mm. Hg, to give finished resin 76.

The resins produced as described above are light colored products having softening points above 80 C. and up to 120 and above, and usually represent yields of 15 to 35% on the hydrocarbon feed. Examples of the preparation and properties of such resins are given in the tables of the foregoing examples.

This application is a continuation of Ser. No. 318,222, filed November 1, 1952, now abandoned.

The nature of the present invention having been thus fully set forth and specific examples of the same given, what is claimed as new and useful and desired to be secured by Letters Patent is:

In a process for the preparation of improved petroleum resins, the combination which comprises isolating a steam cracked hydrocarbon petroleum fraction boiling between about 20 and 140 C., heating said steam cracked fraction to a temperature suflicient to dimerize substantially all cyclodienes, stripping the resulting mixture to a temperature sufiicient to separate an overhead product from the dimerized cyclodienes, said overhead product containing more than 3.5 wt. percent isoprene, fractionating said overhead product to reduce the isoprene content to below about 3.5 wt. percent, recovering a fraction reduced in isoprene content and having the following distillation analysis and composition:

10 Composition Diolefins, Conj 11-25 Isoprene 0-3.5 Piperylene 7-12 Cyclopentadienes 0-2 Others 4-7.5 Aromatics 18-41 Benzene 15-30 Toluene 3-10 C aromatics 1 Paraifins 0-5 Olefins -70 and polymerizing said latter fraction in the presence of an aluminum halide catalyst at a temperature between to C. to produce a resinous product.

References Cited in the file of this patent UNITED STATES PATENTS 1,982,708 Thomas et a1. Dec. 4, 1934 2,734,046 Nelson et a1 Feb. 7, 1956 2,753,325 Banes et al. July 3, 1956 2,753,326 Hamner July 3, 1956 2,754,288 Banes at al July 10, 1956 2,764,577 Hubbard et al. Sept. 25, 1956 2,775,575 Hamner et a1. Dec. 25, 1956 2,775,576 Hamner et al. Dec. 25, 1956 OTHER REFERENCES Thomas et al. (11), Ind. Eng. Chem., 24. 1125-1128 

